Hydrotreating catalyst

ABSTRACT

A CATALYST COMPRISING A LAYERED SYNTHETIC CRYSTALLINE ALUMINOSILICATE CRACKING COMPONENT, PREFERABLY SUBSTANTIALLY FREE OF ANY CATALYTIC METAL OR METALS, DISPERSED IN A GEL MATRIX COMPRISING ALUMINA, A GROUP VI HYDROGENATING COMPONENT AND A GROUP VIII HYDROGENATING COMPONENT, AND PROCESSES USING SAID CATALYST.

United States Patent 3,677,971 HYDROTREATING CATALYST Robert J. White,Pinole, Califi, assignor to Chevron Research Company, San Francisco,Calif. Filed Mar. 9, 1970, Ser. No. 17,626 Int. Cl. B01j 11/40 US. Cl.252-455 R 9 Claims ABSTRACT OF THE DISCLOSURE INTRODUCTION Thisinvention relates to catalytic hydro-cracking of petroleum distillatesand solvent-deasphalted residua to produce high-value fuel products,including jet fuels and gasoline.

PRIOR ART It is known that a catalyst may comprise a crystallinezeolitic molecular sieve component associated with other catalystcomponents. It is also known that at least some of said other catalystcomponents may be in the form of a matrix in which the molecular sievecomponent is dispersed. It is also known that such catalysts may be usedfor such reactions as catalytic cracking, hydrocracking, andhydrodesulfurization. Representative prior patents disclosing one ormore of the foregoing matters include: US. Pats. 3,140,251 and3,140,253; British Pat. 1,056,301; and [French Pat. 1,503,063 and1,506,793.

There has been a continuing search for further improvements in suchcatalysts, and in similar multicomponent catalysts, particularly forhydrocracking and hydrofining uses.

It is also known that a crystalline zeolitic molecular sieve crackingcomponent, while relatively insensitive to organic nitrogen compoundsand ammonia, has a wellordered and uniform pore structure as a result ofthe crystal structure having bonds that are substantially equally strongin three dimensions. This provides definite limitations on the access ofreact-ant molecules to the interiors of the pores.

It is also known, particularly from Granquist US. Pat. 3,252,757, that arelatively new laye'red crystalline aluminosilicate clay-type mineralthat has been synthesized has the empirical formula nSiO A1 0 mlAB xH Owhere the layer lattices comprise said silica, said alumina, and said B,and where n is from 2.4 to 3.0,

m is from 0.2 to 0.6, i

A is one equivalent of an exchangeable cation having valence not greaterthan 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F, 0H",/20" and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3 .5 at 50% relative humidity,

said mineral being characterized by a d spacing at said humidity withinthe range which extends from a lower limit of about 10.4 angstroms to anupper limit of about 12.0 angstroms when A is monovalent, to about 14.7angstroms when A is divalent, and to a value intermediice ate between12.0 angstroms and 14.7 angstroms when A includes both monovalent anddivalent cations. The equivalent of an exchangeable cation, A, in saidmineral may be chosen from the group consisting of H NH Li+, K+, /zCa++,/zMg++, /zSr++, and /2Ba++, and mixtures thereof.

Said layered synthetic crystaline aluminosilicate mineral (hereinafterreferred to for brevity as layered aluminosilicate) in the dehydratedform is known from US. Pat. 3,252,889 to have application as a componentof a catalytic cracking catalyst; however, applications of said layeredaluminosilicate, in either hydrated or dehydrated form, as a componentof a hydrofining or hydrocracking catalyst have not been disclosedheretofore.

OBJECTS In view of the foregoing, objects of the present inventioninclude providing an improved catalyst comprising a cracking componentassociated with other catalyst components that has, compared withsimilar prior art catalysts:

(1) improved hydrocracking activity;

(2) improved hydrodenitrification activity;

(3) improved hydrocracking stability;

(4) improved hydrodenitrification stability;

(5) a cracking component that is crystalline in structure, having poreselongated in two directions, contrary to the pores of crystallinezeolitic molecular sieves, and therefore having less reactant accesslimitations than the pores of such molecular sieves.

DRAWING In the drawing, FIG. 1 is a diagrammatic illustration ofapparatus and flow paths suitable for carrying out the process ofseveral of the embodiments of the present invention, wherein thecatalyst of the present invention is used on a once-through basis toconcurrently hydrocrack and hydrodenitrify a hydrocarbon feedstock toproduce more valuable products, some of which may be further upgraded bycatalytic reforming or catalytic hydrocracking, if desired.

FIG. 2 is a diagrammatic illustration of apparatus and flow pathssuitable for carrying out the process of additional embodiments of thepresent invention, wherein the catalyst of the present invention is usedto concurrently hydrofine and hydrocrack a hydrocarbon feedstock,wherein the hydrofining-hydrocracking zone may be operated on a recyclebasis, and wherein certain portions of the effluent from thehydrofining-hydrocracking zone may be catalytically reformed orcatalytically cracked, as desired.

STATEMENT OF INVENTION In accordance with the present invention, it hasbeen found that the foregoing objects are achieved by a catalystcontaining a unique combination of catalytic components in particularamounts, including alumina, a Group VI component, a Group VHI component,and a layered aluminosilicate component. In preferred embodiments of thepresent invention, said layered aluminosilicate is present in saidcatalyst substantially in the ammonia or hydrogen form and issubstantially free of any catalytic loading metal or metals.

More particularly, in accordance with the present invention there isprovided a catalyst composite comprising:

(A) A gel matrix comprising:

(a) less than 15 weight percent silica,

(b) alumina, in an amount providing an alumina-to-silica weight ratio of50/50 to 100/0,

(c) at least one Group VHI component in the form of metal, oxide,sulfide or any combination thereof, in an amount of 1 to 10 weightpercent, preferably 5 to 9 weight percent, of said matrix, calculated asmetal,

(d) at least one Group VI component in the form of metal, oxide, sulfideor any combination thereof, in an amount of 5 to 25 weight percent,preferably 10 to 20 weight percent, of said matrix, calculated as metal.

(B) A layered aluminosilicate (preferably substantially in the ammoniaor hydrogen form, substantially free of any catalytic loading metal ormetals), said layered aluminosilicate further being in particulate formand being dispersed through said matrix.

Preferably, said catalyst composite will be further characterized by anaverage pore diameter below 100 angstroms and a surface area above 100square meters per gram.

In a preferred embodiment, said catalyst further comprises titanium,zirconium, thorium or hafnium or any combination thereof, in the form ofmetal, oxide, sulfide or any combination thereof, in an amount of 1 to10 weight percent, preferably 5 to 9 weight percent, of said matrix,calculated as metal. Titanium, preferably in the form of titania, ispreferred.

Preferably said gel matrix comprises nickel as the Group VIII componentand tungsten as the Group VI component, in the form of the metals,oxides, sulfides or any combination thereof. Said layeredaluminosilicate may be present in an amount of 1 to 50 Weight percent ofsaid composite.

If desired, said catalyst composite may further comprise a crystallinezeolitic molecular sieve component in the amount of 1 to 50 weightpercent, based on the total catalyst.

Still further in accordance with the present invention, there isprovided a catalyst consisting essentially of:

(A) A porous xerogel comprising:

(a) less than weight percent silica,

(b) alumina, in an amount providing an alumina-tosilica weight ratio of50/50 to 100/0,

(c) nickel, in the form of metal, oxide, sulfide or any combinationthereof, in an amount of l to 10 weight percent, preferably 5 to 9weight percent, of said xerogel, calculated as metal,

((1) tungsten, in the form of metal, oxide, sulfide or any combinationthereof, in an amount of 5 to 25 weight percent, preferably 10 to weightpercent, of said xerogel, calculated as metal,

(e) titanium oxide, in an amount of 1 to 10 weight percent, preferably 5to 9 weight percent, of said xerogel, calculated as metal.

(B) A layered aluminosilicate, in an amount of 1 to 50 weight percent ofsaid catalyst, said layered aluminosilicate preferably beingsubstantially in the ammonia or hydrogen form, and preferably beingsubstantially free of any catalytic loading metal or metals, saidlayered aluminosilicate further being in the form of particles, saidparticles being dispersed through said xerogel; said catalyst having anaverage pore diameter below 100 angstroms and a surface area above 100square meters per gram.

Still further in accordance with the present invention, there isprovided a hydrotreating process which comprises contacting ahydrocarbon feed containing substantial amounts of materials boilingabove 200 F. and selected from the group consisting of petroleumdistillates, solvent-deasphalted petroleum residua, shale oils and coaltar distillates, in a reaction zone with hydrogen and the catalystdescribed above, at hydrotreating conditions including a temperature inthe range 400 to 950 F., a pressure in the range 800 to 3500 p.s.i.g., aliquid hourly space velocity in the range 0.1 to 5.0 and a totalhydrogen supply rate of 200 to 20,000 s.c.f. of hydrogen per barrel offeedstock, and recovering hydrotreated products from said reaction zone.The hydrocarbon feed may contain a substantial amount of organicnitrogen, because the catalyst of the present invention is extremelytolerant of organic nitrogen as well as of ammonia, and because thecatalyst is an efficient hydrodenitrification catalyst. The catalystwill accomplish hydrodenitrification and hydrocracking concurrently andefficiently. The catalyst may be used as a hydrodenitrification catalystin a zone preceding a hydrocracking zone containing a similar ordifferent hydrocracking catalyst. A superior jet fuel product may beproduced when the catalyst is used for hydrocracking a suitablefeedstock. A superior feedstock for a catalytic reformer also may beproduced when the catalyst is used for hydrocracking. The hydrocrackingzone effluent boiling above the gasoline boiling range, or boiling abovethe jet fuel boiling range when a jet fuel product is being recovered,may be catalytically cracked to produce additional valuable products.

The reference to a layered aluminosilicate substantially free of anycatalytic loading metal or metals means that the layered aluminosilicatecontains no more than 0.5 weight percent of catalytic metal or metals,including no more than 0.2 weight percent noble metals, based on thelayered aluminosilicate. The catalytic metal or metals include theGroups IV, VI and VIII metals.

It will be noted that the weight ratio of catalytic metal in thenon-layered-aluminosilicate portion of the catalyst to catalytic metalin the layered aluminosilicate portion of the catalyst is high, in thepreferred catalyst embodiment comprising a layered aluminosilicatesubstantially free of any catalytic metal or metals.

HYDROCARBON FEEDSTOCKS The feedstocks supplied to thehydrofining-hydrocracking zone in the process of the present inventionare selected from the group consisting of petroleum distillates,solvent-deasphalted petroleum residua, shale oils and coal tardistillates. The feedstocks contain substantial amounts of materialsboiling above 200 F., preferably substantial amounts of materialsboiling in the range 350 to 950 F., and more preferably in the range 400to 900 F. Suitable feedstocks include those heavy distillates normallydefined as heavy straight-run gas oils and heavy cracked cycle oils, aswell as conventional FCC feed and portions thereof. Cracked stocks maybe obtained from thermal or catalytic cracking of various stocks,including those obtained from petroleum, gilsonite, shale and coal tar.Because of the superior hydrofining activity and stability of thecatalyst of the present invention, the feedstocks need not be subjectedto a prior hydrofining treatment before being used in thehydrofining-hydrocracking process of the present invention. Feedstocksmay contain as high as several thousand parts per million organicnitrogen, although preferably the organic nitrogen content will be lessthan 1000 parts per million organic nitrogen. Feedstocks also maycontain several weight percent organic sulfur.

CATALYST COMPRISING A LAYERED ALUMINO- SILICATE COMPONENT ANDPREPARATION THEREOF (A) General The layered aluminosilicate component ofthe hydrofining-hydrocracking catalyst may be any catalytically activelayered aluminosilicate, although the synthetic layered aluminosilicateof Granquist US. Pat. 3,252,757 is preferred for use in preparing thecatalyst. The mineral becomes dehydrated during drying and calcinationof the catalyst, as in the examples herein.

(B) Method of preparation The layered aluminosilicate component may bedispersed in a matrix of the other catalyst components by cogelation ofsaid other components around said layered aluminosilicate component in aconventional manner.

The layered aluminosilicate component, substantially in the ammonia orhydrogen form, may be maintained substantially free of any catalyticloading metal or metals, in accordance with a preferred embodiment ofthe present invention, by dispersing it in a slurry of the precursors ofthe other catalyst components at a pH of 5 or above. When a sodium formof layered aluminosilicate is one of the starting materials, it may beconverted to the ammonia or hydrogen form by ion exchange prior to beingcombined with the other catalyst components. Alternatively, it may becombined with the other catalyst components and then converted to theammonia or hydrogen form by ion exchange. In either case, the layeredaluminosilicate component should not be combined with the precursors ofthe other catalyst components at a pH below 5.

The finished catalyst may be sulfided in a conventional manner prior touse, if desired. If not presulfided, the catalyst will tend to becomesulfiled during process operation from any sulfur content that may bepresent in the hydrocarbon feed.

OPERATING CONDITIONS The hydrofining-hydrocracking zone containing thecatalyst of the present invention is operated at a temperature in therange 400 to 950 F, preferably 500 to 850 F., a pressure in the range800 to 3500 p.s.i.g., preferably 1000 to 3000 p.s.i.g., a liquid hourlyspace velocity in the range 0.1 to 5.0, preferably 0.5 to 5.0, and morepreferably 0.5 to 3.0. The total hydrogen supply rate {makeup andrecycle hydrogen) to said zone is 200 to 20,000 s.c.f., preferably 2000to 20,000 s.c.f. of hydrogen per barrel of hydrocarbon feedstock.

The operating conditions in the reforming zone and catalytic crackingzone employed in various embodiments of the present invention areconventional conditions known in the art.

PROCESS OPERATION WITH REFERENCE TO DRAWING Referring now to FIG. 1 ofthe drawing, in accordance with one embodiment of the present invention,a hydrocarbon feedstock as previously described, which in this case mayboil above 400 F. and which may contain a substantial amount of organicnitrogen compounds, is passed through line 1 intohydrofining-hydrocracking zone 2, Which contains the catalyst of thepresent invention. The feedstock is hydrocracked in hydrocracking zone 2at conditions previously described, in the presence of hydrogen suppliedthrough line 3. Under these conditions, concurrent hydrodenitrificationtakes place to the extent that the feedstock is substantiallydenitrified. The efiluent from zone 2 is passed through line 4 toseparation zone 5, from which hydrogen separated from the treatedfeedstock is recycled through line 6 to zone 2. In zone 5, waterentering through line 7 is used to scrub ammonia and other contaminantsfrom the incoming hydrocarbon stream, and the ammonia, water and othercontaminants are withdrawn from zone 5 through line 8. From zone 5, thescrubbed, hydrocracked materials are passed through line 9 todistillation column 10, where they are separated into fractions,including a C -fraction which is withdrawn through line 15, a C -180 F.fraction which is withdrawn through line 16, a l80-400 F. fraction whichis withdrawn through line 17, a 320-5 50 F. fraction which is withdrawnthrough line 18, and a 320 F.+ fraction which is withdrawn through line19. The C 18-0 F. fraction withdrawn through line 16 is asuperior-quality light gasoline. The 180-400" F. fraction withdrawnthrough line 17 is a superior catalytic reforming feedstock, which maybe catalytically reformed in reforming zone 20, from which a superiorcatalytic reformate may be withdrawn through line 25. The 320-550 P.fraction withdrawn through line 18 is a superior-quality jet fuel. The320 F.'+ fraction withdrawn through line 19 is a superior hydrocrackingfeedstock, which may be catalytically hydrocracked in hydrocracking zone26 in the presence of a conventional hydrocracking catalyst and in thepresence of hydrogen supplied to zone 26 through line 27. Fromhydrocracking zone 26, an effluent may be withdrawn through line 28,hydrogen may be separated therefrom in separator 29, and hydrogen may berecycled to hydrocracking zone 26 through line 30. Alternatively, said320" F+ fraction may be catalytically cracked in a catalytic crackingzone under conventional catalytic cracking conditions. From separator29, hydrocracked materials may be passed through lines 35 and 9 todistillation column 10, where they may be separated into fractions, aspreviously described.

Referring now to FIG. 2, a hydrocarbon feedstockk as previouslydescribed, which in this case may boil above 400 F., and which maycontain substantial amounts of organic nitrogen compounds, is passedthrough line 50 to hydrofining-hydrocracking zone 51 containing thecatalyst of the present invention. The feedstock is concurrentlyhydrofined and hydrocracked in zone 51 at conditions previouslydescribed in the presence of hydrogen supplied through line 52. Theefiluent from zone 51 may be passed through line 53 into hydrocrackingzone 54, where it may be hydrocracked under the same conditions as usedin zone 51, in the presence of a hydrocracking catalyst. Thehydrocracking catalyst in zone 54 may be the same catalyst as used inzone 51, or may be a conventional hydrocracking catalyst, for example ahydrocracking catalyst comprising a silica-alumina gel crackingcomponent or a crystalline zeolitic molecular sieve component. If thecatalyst in zone 54 is the same catalyst as in zone 51, or if itcomprises a crystalline zeolitic molecular sieve cracking component, theefiluent from zone 51 may be passed through line 53 into zone 54 withoutintervening impurity removal. If the hydrocracking catalyst in zone 54does not contain a layered aluminosilicate or a molecular sievecomponent, it is preferred that interstage removal of ammonia and otherimpurities be accomplished between zones 51 and 54. Zones 51 and 54 maybe located in separate reactor shells, which may be operated atdifferent pressures. Alternatively, zones 51 and 54 may be separatecatalyst beds located in a single pressure shell 55, and the effluentfrom zone 51 may be passed to zone 54 without intervening pressureletdown, condensation or impurity removal, particularly in the casewhere zone 54 contains the catalyst of the present invention or aconventional catalyst comprising a crystalline zeolitic molecular sievecomponent. The eflluent from zone 54 is passed through line 56 toseparation zone 57, from which hydrogen is recycled through line 58 tohydrofining-hydrocracking zone 51. All or a portion of the recycledhydrogen may be passed through line 59 to hydrocracking zone 54, ifdesired. In separation zone 57, water entering through line 60 is usedto scrub ammonia and other contaminants from the incoming hydrocarbonstream, if these contaminants previously have not been removed betweenzones 51 and 54, and the ammonia, water and other contaminants arewithdrawn from zone 57 through line 65. The effluent from zone 57 ispassed through line 66 to distillation column 67, where it is separatedinto fractions, including a C -fraction which is withdrawn through line68, a C l F. fraction which is withdrawn through line 59, a -400 F.fraction which is withdrawn through line 70, a 320-5 50 F. fractionwhich is withdrawn through line 71, and a 320 F.+ fraction which iswithdrawn through line 72. The fraction withdrawn through line 72 may berecycled through lines 73 and 74 to hydrofining-hydrocracking zone 51,and this is a preferred manner of operation. All or a portion of thefraction in line 73 may be recycled to hydrocracking zone 7 54 throughline 75, if desired. The C 180 F. fraction withdrawn through line 69 isa superior-quality light gasoline. The 180-400 fraction withdrawnthrough line 70 is a superior catalytic reforming feedstock, which maybe catalytically reformed in reforming zone 76, from which a superiorcatalytic reformate may be withdrawn through line 77. The 320-550 F.fraction withdrawn through line 71 is a superior-quality jet fuel. Allor a portion of the 320 F.+ fraction withdrawn through line 72 may bepassed through line 78 to catalytic cracking zone 79, where it may becatalytically cracked under conventional catalytic cracking conditionsin the presence of a conventional catalytic cracking catalyst to producevaluable fuel products, which may be withdrawn from zone 79 through line80'.

EXAMPLES The following examples are given for the purpose of furtherillustrating the catalyst of the present invention, the preparationthereof, and the use thereof in the process of the present invention.

Example 1 A cogelled catalyst (Catalyst A, a comparison catalyst) of thefollowing composition is prepared:

Wt. percent of total Component catalyst NiO 10.5 M 37.5 A1 0 37.5 SiO14.5

Total 100.0

The catalyst is prepared by the following steps, using sufiicientquantities of the various starting materials to produce theabove-indicated weight percentages of the components of the finalcatalyst:

(1) An aqueous acidic solution is prepared, containing AlCl NiCl andacetic acid.

(2) Three alkaline solutions are prepared: (1) a sodium silicatesolution; (2) an ammonium molybdate solution; and (3) an ammoniasolution containing sufiicient excess ammonia so that upon combining thealkaline solutions with the acidic solution coprecipitation of all ofthe metal-containing components of the solutions will occur at a neutralpH of about 7.

(3) The aidic and alkaline solutions are combined, and coprecipitationof all of the metal-containing components of the solutions occurs at apH of about 7, resulting in a slurry.

(4) The slurry is filtered to produce a hydrogel filter cake, which iswashed repeatedly with dilute ammonium acetate solution, to removesodium and chloride ionic impurities from the hydrogel.

(5) The hydrogel is dried in an air-circulating oven and then isactivated in flowing air for 5 hours at 950 F.

The finished catalyst is characterized by a surface area of above 200 m./g., an average pore diameter of below 100 angstroms, and a bulk densityof 0.9+ gram of catalyst per pubic centimeter of reactor space occupiedby the catalyst.

Example 2 A cogelled catalyst (Catalyst B, a catalyst according to thepresent invention) of the following composition is prepared:

Wt. percent of total Componentcatalyst NiO 9.6 M00 33.7 A1 0 33.7 SiO13.0 Layered crystalline clay-type aluminosilicate 10.0

Total 100.0

The catalyst is prepared exactly as in Example 1, using sufiicientquantities of the various starting materials to produce theabove-indicated weight percentages of the components of the finalcatalyst. The catalyst contains the same proportions of non-layered claycomponents as the catalyst of Example 1.

The ammonium form of the layered crystalline claytype aluminosilicatecomponent, in finely divided form, is added to the washed hydrogelreferred to in Step 4 of Example 1.

The finished catalyst is characterized by a surface area above 100 m./g., an average pore diameter below 100 angstroms, and a bulk density of0.9 gram of catalyst per cubic centimeter of reactor space occupied bythe catalyst.

Example 3 Portions of Catalysts A and B of Examples 1 and 2,respectively, are crushed to 16-28 mesh and are separately used tohydrocrack separate portions of a catalytic cycle oil feedstock derivedfrom a California crude oil, on a once-through basis.

The cycle oil feedstock has the following characteristics:

The hydrocracking activities of the two catalysts, as measured by thestarting temperatures necessary to achieve the indicated per-passconversion, are:

Catalyst- Starting T, F. A 765 B 765 The 300-500 F. jet fuel boilingrange product in each case is of the same adequate quality, in that ineach case the smoke point is 15-20 mm. and the freeze point is below F.

The hydrocracked liquid product in each case is essentially free oforganic nitrogen compounds, indicating that essentially completehydrodenitrification accompanies the hydrocracking in each case.

Example 4 Additional portions of Catalysts A and B of Examples 1 and 2,respectively, are crushed to 16-28 mesh and are separately used tohydrodenitrify separate portions of the same catalytic cycle oil used inExample 3.

The hydrodenitrification conditions are:

Total pressure, p.s.i.g 1200 Total hydrogen rate, s.c.f./bbl 5000 Liquidhourly space, velocity, v./v./hr. 1.25 Product nitrogen, p.p.m 1

The results are tabulated below, together with the bulk densities of thecatalysts:

Catalyst Catalyst bulk fouling Starting density, rate, T in WeightCatalyst g./cc. F./hr. F./hr. ratio 2 Example 1 Hydrodenltrificatlonactivity. 320500 F. product 320 F. product 9 CONCLUSIONS Applicant doesnot intend to be bound by any theory for the unexpectedly superiorhydrofining and hydrocracking activity of the catalyst of the presentinvention. Applicant assumes that the favorable results are largelyattributable to, and unique to, the particular combination of catalyticcomponents used, coupled with a low catalyst silica content and lowcatalyst bulk density.

What is claimed is:

1. A catalyst composite comprising:

(A) a gel matrix comprising:

' (a) less than 15 weight percent silica,

:(b) alumina, an amount providing an alumina-tosilica weight ratio of50/50 to 100/0,

(c) a Group VIII component, in the form of metal, oxide, sulfide or anycombination thereof, in an amount of 1 to 10 weight percent of saidmatrix, calculated as metal,

(d) a Group VI component, in the form of metal, oxide, sulfide or anycombination thereof, in an amount of to 25 weight percent of saidmatrix, calculated as metal;

(B) a layered crystalline aluminosilicate clay-type mineral inparticulate form dispersed through said matrix, said mineral having theempirical formula:

nSiO A1 0 mAB xH O where the layer lattices comprise said silica, saidalumina, and said B, and where n is from 2.4 to 3.0,

m is from 0.2 to 0.6,

A is one equivalent of an exchangeable cation hav-- ing a valence notgreater than 2, and is external to the lattice,

'B is chosen from the group of negative ions which consists of F-, OH",V20- and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50% relative humidity,

said mineral being characterized by a d spacing at said humidity withinthe range which extends from a lower limit of about 10.4 A. to an upperlimit of about 12.0 A. when A is monovalent, to about 14.7 A. when A isdivalent, and to a value intermediate between 12.0 A. and 14.7 A. when Aincludes both monovalent and divalent cations.

2. A catalyst composite as in claim 1, wherein said layered crystallinealuminosilicate clay-type mineral is present in an amount of 1 to 50weight percent, based on said composite.

3. A catalyst composite as in claim 1 wherein said layered crystallinealuminosilicate clay-type mineral is substantially in the ammonia orhydrogen form, and is substantially free of any catalytic loading metalor metals.

4. A catalyst composite as in claim 1, wherein said gel matrix comprisesnickel and tungsten, in the form of the metals, oxides, sulfides or anycombination thereof.

5. A catalyst composite as in claim 1, further comprising titanium,zirconium, thorium or hafnium, or any combination thereof in the form ofthe metal, oxide, sulfide or any combination thereof, in an amount of 1to weight percent of said matrix, calculated as metal.

6. A catalyst composite as in claim 5, wherein said titanium is in theform of titania.

7. A catalyst composite as in claim 1, further comprising a crystallinezeolitic molecular sieve component in an amount of 1 to 50 weightpercent, based on said composite.

8. A catalyst composite as in claim 1, characterized by an average porediameter below angstroms and a surface area above 100 square meters pergram.

9. A catalyst consisting essentially of:

(A) a porous xerogel comprising:

(a) less than 15 weight percent silica,

(b) alumina, in an amount providing an aluminato-silica weight ratio of50/50 to 100/0,

(0) nickel, in the form of metal, oxide, sulfide or any combinationthereof, in an amount of 1 to 10 weight percent of said xerogel,calculated as metal,

(d) tungsten, in the form of metal, oxide, sulfide or any combinationthereof, in an amount of 5 to 25 Weight percent of said xerogel,calculated as metal,

(e) titanium oxide, in an amount of l to 10 weight percent of saidxerogel, calculated as metal;

(B) a layered crystalline aluminosilicate clay-type mineral, in anamount of l to 50 weight percent of said catalyst, said mineral being inthe form of particles, said particles being dispersed through saidxerogel, said mineral having the empirical formula:

nSiO A1 0 mAB xH 0 where the layer lattices comprise said silica, saidalumina, and said B, and where n is from 2.4 to 3.0,

m is from 0.2 to 0.6,

A is one equivalent of an exchangeable cation having a valence notgreater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F-, OH,VzO-- and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50% relative humidity,

said mineral being characterized by a d spacing at said huimdity withinthe range which extends from a lower limit of about 10.4 A. to an upperlimit of about 12.0 A. when A is monovalent, to about 14.7 A. when A isdivalent, and to a value intermediate between 12.0 A. and 14.7 A. when Aincludes both mono valent and divalent cations;

said catalyst having an average pore diameter below 100 A. and a surfacearea above 100 square meters per gram. References Cited UNITED STATESPATENTS 3,546,094 12/ 1970 Jatfe 252-455 R 3,535,229 '10/1970 Jafie etal. 252-455 R 3,535,228 10/ 1970 Csicsery et al. 252-455 R 3,560,370 2/1971 Billon et al. 252-455 R CARL F. DEBS, Primary Examiner US. Cl. X-R.208-1. 11

